CN104069783B - A kind of preparation method of composite micro-capsule of carbon nano-tube modification - Google Patents
A kind of preparation method of composite micro-capsule of carbon nano-tube modification Download PDFInfo
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Abstract
The preparation method of the composite micro-capsule of a kind of carbon nano-tube modification provided by the invention, comprises the following steps: the modification of CNT: CNT is obtained modified carbon nano-tube successively after acidifying, chloride, grafting; Modified carbon nano-tube and phase-change material compound: modified carbon nano-tube is mixed with the phase-change material after thawing, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in phase-change material, obtain composite phase-change material; The preparation of composite phase-change microcapsules: by macromolecule wall material performed polymer, composite phase-change material, emulsifying agent, deionized water mixing, adjust pH, react and get final product.CNT combines with microcapsules technology by the method, utilizes the CNT of modification to improve the heat conduction of phase-change material, utilizes microcapsules technology to solve the leakage problem of phase-change material, thus reach the object solving low, the easy leakage problem of phase-change material heat conduction.
Description
Technical field
The invention belongs to Material Field, particularly a kind of preparation method of composite micro-capsule of carbon nano-tube modification.
Background technology
Resource, lack of energy crisis and problem of environmental pollution more and more receive the concern in the world; energy use efficiency is improved under guarantee certain mass condition; exploitation regenerative resource has become the vital task faced by human needs simultaneously; phase change energy storage technology can solve energy supply and demand unmatched contradictory problems over time and space, so be the effective means improving energy utilization rate.
When the phase transition process of phase-change material betides solid-liquid phase change, solid-solid phase change usually, it is that a class can undergo phase transition in a certain temperature range thus absorb and discharge the material of latent heat of phase change, so can reach the object of phase-change accumulation energy by inhaling heat release.
Microcapsules technology by coated for phase transformation capsule material, thus can well solve phase-change material leakage problem in use.
Chinese patent literature CN101407714A describes a kind of paraffinic based carbon nano-tube compound phase transformation heat accumulating, phase-change heat-storage material is compounded to form by the CNT after ball milling and paraffin, although CNT add the heat conduction that improve phase-change material, but it is not described the dispersiveness of CNT in paraffin, do not propose how to solve phase-change material leakage problem in use simultaneously yet.Patent document CN102504766A describes the micro-preparation method and application of a kind of phase-change accumulation energy, it is shell material that patent document CN101670256A describes a kind of polymer, phase-change material paraffin is the microcapsule preparation method of core, although well solved the leakage problem of phase-change material by microcapsules technology, still do not solve the lower problem of microcapsules heat conduction.CNT combines with microcapsules technology by the present invention, first modification is carried out to CNT, utilize the CNT of modification to improve the heat conduction of phase-change material, utilize microcapsules technology to solve the leakage problem of phase-change material, thus it is low to reach the heat conduction of solution phase-change material, the object of easy leakage problem.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of composite micro-capsule of carbon nano-tube modification.
Technical scheme: the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification provided by the invention, comprises the following steps:
(1) modification of CNT: CNT is obtained modified carbon nano-tube successively after acidifying, chloride, grafting;
(2) modified carbon nano-tube and phase-change material compound: modified carbon nano-tube is mixed with the phase-change material after thawing, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in phase-change material, obtain composite phase-change material;
(3) preparation of macromolecule wall material performed polymer: after urea and formaldehyde mixing, regulate pH to 8-9, stirring reaction secures satisfactory grades sub-wall material performed polymer;
(4) preparation of composite phase-change microcapsules: by macromolecule wall material performed polymer, composite phase-change material, emulsifying agent, deionized water mixing, adjust pH to 1-3, stirring reaction, isothermal curing, to obtain final product.
Step (1) is specially: CNT is being 1:(2-4 containing volume ratio) red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed acid solution in reflux acidification reaction 5-7h, product is 60-80 DEG C of acyl chloride reaction 12-36h in thionyl chloride, product again with fatty alcohol 60-80 DEG C of graft reaction 24-72h; Wherein, the amount ratio of CNT and mixed acid solution is 5g:(600-800) ml, the amount ratio of CNT and thionyl chloride is 1g:(40-60) ml, and the amount ratio of CNT and fatty alcohol is 1g:(5-20) g.
Wherein, described fatty alcohol is the fatty alcohol of a carbon number 8-18 carbon, preferred n-octyl alcohol, tetradecyl alchohol or octadecyl alcolol.
In step (2), phase-change material is paraffin, palmitic acid or aliphatic acid.
In step (2), the amount ratio of modified carbon nano-tube and phase-change material is (1-4): (96-99).
In step (3), the amount ratio of described urea and formaldehyde is 1:(1-2); Reaction temperature is 70-90 DEG C, and the reaction time is 1-3h.
In step (4), reaction temperature is 50-100 DEG C, and the reaction time is 2-4h, and mixing speed is 450-2000r/min.
In step (4), described emulsifying agent is maleic anhydride of styrene, APES or neopelex.
In step (4), the amount ratio of macromolecule wall material, composite phase-change material, emulsifying agent, deionized water is 1:(0.5-2): (0.1-1): (50-100).
Beneficial effect: CNT combines with microcapsules technology by the preparation method that the invention provides composite micro-capsule, utilize modified CNT and phase-change material compound, and form high-heat-conducting composite phase-transition microcapsules by microcapsules technology, the CNT of modification is utilized to improve the heat conduction of phase-change material, utilize microcapsules technology to solve the leakage problem of phase-change material, thus reach the object solving low, the easy leakage problem of phase-change material heat conduction.
Accompanying drawing explanation
Fig. 1 is the dispersed effectiveness comparison figure of CNTs-C18 and CNTs that the present invention obtains; Wherein, a left side is CNTs-C18, and the right side is CNTs.
Detailed description of the invention
Below in conjunction with accompanying drawing the present invention made and further illustrating.
The modification of embodiment 1 CNT
Preparation mixed acid solution: be the red fuming nitric acid (RFNA) of 69% of 1:3 and the concentrated sulfuric acid mixing of 98% by volume ratio, obtain mixed acid solution.
5g CNT CNTs and 700ml mixed acid solution are blended in return stirring 6h in oil bath.Be cooled to room temperature, be washed till neutrality with distilled water, then suction filtration, obtain the CNT CNTs-COOH after acidifying after drying, by CNTs-COOH and SOCl
2(amount of CNTs-COOH is in CNTs, CNTs-COOH and SOCl
2amount ratio be 1:50 (g/ml)) 70 DEG C stir 24h, steam SOCl
2product is washed till neutrality, the CNTs-COCl of chloride is obtained after dry 24h, (amount of CNTs-COCl is in CNTs for CNTs-COCl after chlorination and octadecyl alcolol, the mass ratio of CNTs-COCl and octadecyl alcolol is 1:10, stir 48h at 70 DEG C, washing drying obtains modified carbon nano-tube CNTs-C18.
The modification of embodiment 2 CNT
Preparation mixed acid solution: be the red fuming nitric acid (RFNA) of 69% of 1:2 and the concentrated sulfuric acid mixing of 98% by volume ratio, obtain mixed acid solution.
5g CNT CNTs and 800ml mixed acid solution are blended in return stirring 5h in oil bath.Be cooled to room temperature, be washed till neutrality with distilled water, then suction filtration, obtain the CNT CNTs-COOH after acidifying after drying, by CNTs-COOH and SOCl
2(amount of CNTs-COOH is in CNTs, CNTs-COOH and SOCl
2content be 1:40 (g/ml)) 60 DEG C stir 36h, steam SOCl
2, product is washed till neutrality, after dry 24h, obtains the CNTs-COCl of chloride, (amount of CNTs-COCl is in CNTs for CNTs-COCl after chlorination and n-octyl alcohol, the mass ratio of CNTs-COCl and n-octyl alcohol is 1:20, stirs 72h at 60 DEG C, and washing drying obtains modified carbon nano-tube CNTs-C8.
The modification of embodiment 3 CNT
Preparation mixed acid solution: be the red fuming nitric acid (RFNA) of 69% of 1:4 and the concentrated sulfuric acid mixing of 98% by volume ratio, obtain mixed acid solution.
5g CNT CNTs and 600ml mixed acid solution are blended in return stirring 6h in oil bath.Be cooled to room temperature, be washed till neutrality with distilled water, then suction filtration, obtain the CNT CNTs-COOH after acidifying after drying, by CNTs-COOH and SOCl
2(amount of CNTs-COOH is in CNTs, CNTs-COOH and SOCl
2content to be 1:60 (g/ml) stir 12h at 80 DEG C, steam SOCl
2, product is washed till neutrality, after dry 24h, obtains the CNTs-COCl of chloride, (amount of CNTs-COCl is in CNTs for CNTs-COCl after chlorination and tetradecyl alchohol, the mass ratio of CNTs-COCl and tetradecyl alchohol is 1:5, stirs 24h at 80 DEG C, and washing drying obtains modified carbon nano-tube CNTs-C14.
The preparation of embodiment 4 phase-change microcapsule
Mixed than 2:3 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 8.5, and under 80 DEG C and 600r/min stirring condition, react 1h, secure satisfactory grades sub-wall material performed polymer.
Pour in 2g water-soluble transparent polymer wall material performed polymer after paraffin after 1g maleic anhydride of styrene, 1g being melted mixes with 100ml distilled water, 1000r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 2 at about 30min, be incubated 70 DEG C of reaction 3h, be warming up to 85 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
The preparation of embodiment 5 phase-change microcapsule
Mixed than 1:1 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 9.0, and under 90 DEG C and 600r/min stirring condition, react 2h, secure satisfactory grades sub-wall material performed polymer.
By mass ratio be 1:99 modified carbon nano-tube CNTs-C18 with melt after paraffin mix, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in paraffin, obtain CNTs-C18/ paraffin composite;
0.1g maleic anhydride of styrene, 1gCNTs-C18/ paraffin composite are poured in 0.5g water-soluble transparent polymer wall material performed polymer after mixing with 50ml distilled water, 1500r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 2 at about 30min, be incubated 70 DEG C of reaction 3h, be warming up to 85 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
The preparation of embodiment 6 phase-change microcapsule
Mixed than 1:2 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 8.0, and under 70 DEG C and 600r/min stirring condition, react 3h, secure satisfactory grades sub-wall material performed polymer.
By mass ratio be 2:98 modified carbon nano-tube CNTs-C18 with melt after paraffin mix, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in paraffin, obtain CNTs-C18/ paraffin composite;
0.5g maleic anhydride of styrene, 1gCNTs-C18/ paraffin composite are poured in 1g dissolubility transparent polymer wall material performed polymer after mixing with 80ml distilled water, 1000r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 2 at about 30min, be incubated 70 DEG C of reaction 3h, be warming up to 85 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
The preparation of embodiment 7 phase-change microcapsule
Mixed than 2:3 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 8.5, and under 80 DEG C and 600r/min stirring condition, react 1h, secure satisfactory grades sub-wall material performed polymer.
By mass ratio be 3:97 modified carbon nano-tube CNTs-C18 with melt after paraffin mix, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in paraffin, obtain CNTs-C18/ paraffin composite;
0.5g APES, 1gCNTs-C18/ paraffin composite are poured in 1g dissolubility transparent polymer wall material performed polymer after mixing with 100ml distilled water, 450r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 2 at about 30min, be incubated 70 DEG C of reaction 3h, be warming up to 85 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
The preparation of embodiment 8 phase-change microcapsule
Mixed than 2:3 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 8.5, and under 80 DEG C and 600r/min stirring condition, react 1h, secure satisfactory grades sub-wall material performed polymer.
By mass ratio be 4:96 modified carbon nano-tube CNTs-C18 with melt after paraffin mix, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in paraffin, obtain CNTs-C18/ paraffin composite;
0.5g DBSA, 1gCNTs-C18/ paraffin composite are poured in 1g dissolubility transparent polymer wall material performed polymer after mixing with 50ml distilled water, 2000r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 2 at about 30min, be incubated 70 DEG C of reaction 3h, be warming up to 85 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
The preparation of embodiment 9 phase-change microcapsule
Mixed than 2:3 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 8.5, and under 80 DEG C and 600r/min stirring condition, react 1h, secure satisfactory grades sub-wall material performed polymer.
By amount ratio be 4:96 modified carbon nano-tube CNTs-C14 with melt after palmitic acid mix, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in paraffin, obtain CNTs-C14/ palmitic acid composite;
1g DBSA, 1gCNTs-C14/ palmitic acid composite are poured in 1g dissolubility transparent polymer wall material performed polymer after mixing with 100ml distilled water, 1000r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 1 at about 30min, be incubated 50 DEG C of reaction 4h, 50 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
The preparation of embodiment 10 phase-change microcapsule
Mixed than 2:3 by amount of substance with formaldehyde by urea in there-necked flask, after urea dissolves, adjust ph is 8.5, and under 80 DEG C and 600r/min stirring condition, react 1h, secure satisfactory grades sub-wall material performed polymer.
By amount ratio be 4:96 modified carbon nano-tube CNTs-C8 with melt after stearic acid mix, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in paraffin, obtain CNTs-C8/ stearic acid composite;
1g DBSA, 1gCNTs-C8/ stearic acid composite are poured in 1g dissolubility transparent polymer wall material performed polymer after mixing with 100ml distilled water, 1000r/min high-speed stirred emulsification 15min, slowly dripping the dilute sulfuric acid of 2%, system pH is made to be reduced to 3 at about 30min, be incubated 100 DEG C of reaction 2h, 100 DEG C solidification 1h, after washing at 50 DEG C dry 24h, obtain phase-change microcapsule after grinding.
Measure the thermal conductivity factor of the phase-change microcapsule of embodiment 4 to 10, the results are shown in Table 1.
The different CNT amount of table 1 adds the thermal conductivity factor of rear composite phase-change microcapsules
Claims (9)
1. a preparation method for the composite micro-capsule of carbon nano-tube modification, is characterized in that: comprise the following steps:
(1) modification of CNT: be 1:(2-4 containing volume ratio by CNT) red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed acid solution in reflux acidification reaction 5-7h, product is 60-80 DEG C of acyl chloride reaction 12-36h in thionyl chloride, product again with fatty alcohol 60-80 DEG C of graft reaction 24-72h; Wherein, the amount ratio of CNT and mixed acid solution is 5g:(600-800) ml, the amount ratio of CNT and thionyl chloride is 1g:(40-60) ml, and the amount ratio of CNT and fatty alcohol is 1g:(5-20) g;
(2) modified carbon nano-tube and phase-change material compound: modified carbon nano-tube is mixed with the phase-change material after thawing, higher than ultrasonic under phase transition temperature, make modified carbon nano-tube dispersed in phase-change material, obtain composite phase-change material;
(3) preparation of macromolecule wall material performed polymer: after urea and formaldehyde mixing, regulate pH to 8-9, stirring reaction secures satisfactory grades sub-wall material performed polymer;
(4) preparation of composite phase-change microcapsules: by macromolecule wall material performed polymer, composite phase-change material, emulsifying agent, deionized water mixing, adjust pH to 1-3, stirring reaction, isothermal curing, to obtain final product.
2. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: described fatty alcohol is the fatty alcohol of a carbon number 8-18 carbon.
3. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 2, is characterized in that: described fatty alcohol is n-octyl alcohol, tetradecyl alchohol or octadecyl alcolol.
4. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: in step (2), and phase-change material is paraffin or aliphatic acid.
5. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: in step (2), and the amount ratio of modified carbon nano-tube and phase-change material is (1-4): (96-99).
6. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: in step (3), and the amount ratio of described urea and formaldehyde is 1:(1-2); Reaction temperature is 70-90 DEG C, and the reaction time is 1-3h.
7. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: in step (4), and reaction temperature is 50-100 DEG C, and the reaction time is 2-4h, and mixing speed is 450-2000r/min.
8. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: in step (4), and described emulsifying agent is maleic anhydride of styrene, APES or neopelex.
9. the preparation method of the composite micro-capsule of a kind of carbon nano-tube modification according to claim 1, is characterized in that: in step (4), the amount ratio of composite phase-change material, macromolecule wall material performed polymer, emulsifying agent, deionized water is 1:(0.5-2): (0.1-1): (50-100).
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| CN104762066B (en) * | 2015-03-06 | 2019-01-08 | 深圳大学 | Compound microcapsules of storing energy through phase change and preparation method thereof |
| CN104962240A (en) * | 2015-05-18 | 2015-10-07 | 西安工程大学 | Preparation method of nano particle-doped phase change microcapsule |
| CN104830278B (en) * | 2015-05-20 | 2018-08-24 | 沈阳化工研究院有限公司 | A kind of improved silica shape-stabilized phase change energy storage and preparation method thereof |
| CN105670568B (en) * | 2016-01-04 | 2018-08-21 | 深圳大学 | A kind of preparation method of butyl stearate carbon nanotube microcapsule |
| CN105950121B (en) * | 2016-06-30 | 2019-10-15 | 中山火炬职业技术学院 | A kind of intelligent adjustable phase-change material and preparation method thereof of Nano capsule |
| CN106757497A (en) * | 2016-12-06 | 2017-05-31 | 太仓大唐化纤厂 | A kind of preparation method of long acting antibiotic phase-changing and temperature-regulating fiber and Microencapsulated Phase Change Materials |
| CN106732219B (en) * | 2016-12-08 | 2019-02-26 | 辽宁石油化工大学 | A kind of carbon nanotube/paraffin microcapsule preparation method with photo absorption performance |
| CN110373162B (en) * | 2019-07-10 | 2021-03-09 | 浙江工业大学 | Carbon nanotube modified phase change microcapsule and preparation method thereof |
| CN111876223B (en) * | 2020-08-05 | 2022-08-02 | 扬州工业职业技术学院 | Modified carbon nanotube ionic liquid lamellar liquid crystal lubricant and preparation method thereof |
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